Production of o.o-dialkylphosphoric acid esters of substituted halogenbutenols



United States Patent lice PRODUCTION OF 0.0-DIALKYLPHOSPHORIC ACID ESTERS OF SUBSTITUTED HALOGEN- BUTENOLS- Heinz Pohlemann, Ludwigshafen (Rhine), Herbert Stummeyer, Mannheim, and Heinrich Adolphi, Limburgerhof, Germany, assignors to Badische Anilin- & Soda- Fabrik Aktiengesellschaft, Ludwigshafen (Rhine), Germany No Drawing. Application January 6, 1958 Serial No. 707,118

12 Claims. (Cl. 260-461) The present invention relates to a process for the production of new triesters of ortho-phosphoric acid or of ortho-thionophosphoric acid. More specifically it relates to the production of new 0.0-dialkylphosphoric or 0.0-dialkylthionophosphoric acid esters of substituted halogen-butenols.

It is known that triesters of phosphoric acid are obtained by reacting dialkoxyphosphoric acid monohalides or dialkoxythiophosphoric acid monohalides with alcohols or phenols. Thus from the U.S. patent specification No. 2,536,647 it is known for example, to cause the alkali salt of para-nitrophenol to act on the bis-(betachlorethyl)-thiophosphoryl chloride obtainable by the reaction of sulfur with chlor-bis-(beta-chlorethyl)-phosphite, bis-(beta-chlorethyl)-para-nitrophenyl-thionophosphate being formed. The alcohols used for the reaction Patented Dec. 29, 1959 portance for many applications. They are eflicient insecticides and rodent-destroying agents. They can also be used as corrosion preventives, flameproofing agents, flotation agents, plasticizers'or as additives for high pressure lubricants. 1 I l The main object of the present invention is the production of new QO-dialkylpho'sphoric acid esters (which term is hereinafter to be understood as including also 0.0-dialkylphosphoric acid esters) which have an outstanding effect as insecticides for practically all types of insects, especially sucking insects, such as aphides; Furthermore, the newsubstances have a destructive effect on eggs and larvae of the said pests, but do not affect warmblooded animals except to a negligible degree. A further object of the invention is the production of such 0.0- dialkylphosphoric acid esters as have a pronounced systemic action, i.'e. the phosphoric acid ester is conveyed through the system of the plants to be protected against pests, without losing its action.

Yet another object of the invention is the provision of a simple and efiicient process for making the said new phosphoric acid esters with good yield.

We have found that the said objects are achieved and new 0.0.-dialkylphosphoric acid esters of substituted halogcn-butanols are obtained by reacting an 0.0-dialkylv phosphoric acid monohalide of the general formula:

with phosphoric acid ester halides have been chosen from among saturated, unsaturated, straight-chain and branched-chain alcohols or thioalcohols. For example, by the reaction of methallyl alcohol or the alkali salts thereof with phosphoric acid ester halides, such as O monoor 0.0-di-alkylphosphoric acid halides, the-corinwhich X is an oxygen or sulfur atom, Hal-is a halogen atom, and R and R represent lower saturated aliphatic hydrocarbon radicals with 1 to 4 carbon atoms, with a 3-halogen-butane-(3) ol-(2) substituted in l-position of the formula: 7

Hal H0CH('J=GH2 H'YZ in which Hal isa halogen atom, Z represents a hydrogen 7 atom or a saturated or unsaturated aliphatic hydrocarbon rated, and R R R R and R are hydrogen atoms or alkyl, alkenyl, aryl, cycloalkyl, cycloalkenyl, aralkyl, aralkenyl or heterocyclic radicals which may be substituted by further radicals, such as halogen, nitro or amino groups, by reacting phosphorous o'xy-halides of the gen eral formula: v I

X' O=PY in which Z is a halogen atom and X and Y have the above significance, with an allyl typealcohol of the, formula lib R1-o=0( J-0H MR2 R3 Rs in which R R R R and R have the meaning defined -above, at temperatures of minus 25 C. to about minus 70 C. g Many of the triesters of phosphoric acidalreadypreradical with 1 to 4 carbon atoms and Y is an oxygen or sulfur atom, a sulfone or sulfoxy group or an --NH-- group. v

The resultant new 0.0-dialkylphosphoric acid esters of 3-halogen-butene-(3)-ols substituted in l-position have the following general constitution:

RO\ /X P/ I rv-o o-on-d onr CHr-YZ in which R, R, X, Hal, Y and Z have the above significance.

' Suitable 3-halogen-butene-(3)-ol-(2) compounds substituted in l-position are for example 1-alkoxy-3-halogenbutene- 3 -ol and 1-alken0xy-3 -halogen-butene- 3 -ols whose alkyl or alkenyl groups consist of 1 to 4 carbon atoms. Suitable compounds are for example l-methoxy- 3-chlorbutene- (3 -0l- (2) 1-methoxy-3 -brornbutene-(3 ol-(2), 1-methoxy-3-iodobutene-(3)-ol 2), and also the corresponding 1-ethoxy-, 1-propoxy, l-butoxyand the 1- allyloxyderivatives of 3-chlor, 3 -brom.--or 3-iodo butene-(3)-ol-( 2). Particularly suitable arealso the derivatives of 3-halogen-butene-(3)-ol-(2) which contain in 1 position an. alkylor alkenyl mono-substituted amino pared in great numbers have gained considera];l e :irn;

group ofwhich the alkyl or alkenyl radical contains 1 to 4 carbon atoms. As representatives of, suchgcompounds. there may be mentioned, for example, 1-methylamino-, l-ethylaminol-propylaminoand l-butylarnino- 3-chlorbutene-( 3 -ol- (2) and .1 al1ylamino-3 chlorbutene (3)-ol-(2). l-amino-3-chlorbutene-(3)-ol-(2) is also suitable.

Of the 3-halogen-butene-(3)-o1-(2) compounds which are substituted in l-position byan aliphatic thiol group, for example by an alkyl or alkenyl mercapto radical (in which the sulfur atonrmay be oxidized to a sulfoxy or sulfone group). and their alkylor alkenyl groups may contain l to 4 carbon atoms there may be mentioned, for example, '1-ethyhnercapto-, l-ethylsulfoxyand 1- ethyl-sulfonyl-3 -chlorbutene-( 3 -ol-. 2)

Of the 0.0-dialkylphosphoric acid monohalides to be used as the second reaction component the chlorides, bromides and iodides of 0.0-dialkylphosphoric acids and 0.0-dialltylthionophosphoric acids are especially suitable. The Qo-dialkylphosphoric acid monohalides are'readily available compounds; For example, they can be obtained' by reaction ofphosphorus oxychloride or phos phorus thiotrichloride with the'calculated amount of aliphatic monohydric alcohols. As representatives of these reaction components there may be mentioned above all dimethoxyphosphoric acid rn'onochloride, dimethoxyphosphoric acid monobromide, dimethoxyphosphoric acid mon'oiodide, and also the'corresponding halides of 0.0- diethyl-, 0.0-.dipropyland 0.0-dibutyl-phosphoric acid as well as the chlorides, bromides and diodides of 0.0-dimethylthionophosphoric acid, 0.0-diethylthionophosphoric acid, 0.0-dipropylthionophosphoric acid and 0.0- dibutylthionophosphoric acid.

The reacti'onis carried out by causing the two reaction components to act on each other. In general it is immaterial which component is added to the other. It is advantageous to add the dialkylphosphoric acid mono halide to the 3-halogen-butene-(3)-ol-(2) substituted in l-position. The initial materials are used in about the equivalent amounts. ,Sometimes it may be advantageous, however, to useone or other initial material in a slight excess, for'example of l to Working in the presence of an inert organic diluent may be preferable in some cases. Hydrocarbons, such as benzene, toluene, xylene, gasolines and cyclohexane or chloro'hydrocarbons, as for example methylene chloride, chloroform, or ethylene chloride or carbon tetrachloride may serve for example as diluents. The amount of a diluent, when such co-employed, is not critical and may vary within wide limits. In'general only so much of these substances is used as is necessaryto achieve an intimate mixing of the reaction component's. Although the reaction occurs appreciably even at low temperatures, it is preferable to work at elevated temperatures, for example from about to 120 C., and advantageously between about 40 and 50 C.

It is good practice to carry out the reaction in the presence of an agent capable of binding hydrogen halide, as for example pyridine, or. other tertiary amines, having a boiling point above the reaction temperature, for example triethylamine or tributylamine, in order to bind the hydrogen halide set free during the reaction. Alkali carbonates or alkali bicarbonates may becoernployed for this purpose. Accordingly, the agents which bind"hydrogen halide are preferably used in amounts which are equimolar to the 0.0-dialkylphosphoric acid monohalides to be reacted. e i I The procedure in the reaction of the two reaction components may be, for example, to dissolve the substituted 3-halogen-butene-(3)-ol-(2) in one of the said diluents, to add "to this' solution the substance binding "hydrogen halide and then to slowly introduce into this mixture the molar amounfiof the dialkylphosphoric acid monohalide corresponding to the halogen-butenol. To speed up the reaction it is advantageous to'stir the components and to prevent a higher concentration of the phosphoric acid halide occurring locally anywhere in the reaction "mix- The new Qo-dialkylphosphoric acid esters of the substituted halogen-butenols are highly eflicient insecticides and ovicides. Moreover, part of them have a markedly good systemic action. The esters are less toxic for warmblooded animals than the'conventional phosphoric acid ester type insecticides.

The following examples will further illustrate this invention but the invention is not restricted to these examples. The parts given in the examples are parts by weight.

Example 1 56.4 parts of diethoxythionophosphric acid monochlo- V ride are allowed to flow slowly at about 40 C. into a mixture of 40.8 parts of 1-methoxy-3-chlorbutene-(3)- ol-(Z) and 23.7 parts of anhydrous pyridine with powerful stirring. After the addition is completed the whole is further stirred for about 5 hours at to C. in order to complete the reaction. The reaction mixture is then cooled toroom temperature, and 30 to 40 parts of water and parts of benzene are added thereto. After stirring the mixture thoroughly the non-aqueous layer is separated in a separating funnel. The separated layer is shaken with a little diluted hydrochloric acid and then with water, then dried over sodium sulfate and distilled. 75 parts of a compound of the boiling point 96 C. at 0.001 mm. Hg pressure are obtained as a colorless oil. The compound has the formula:

CaHsO S P-O-CH-CHaO-OH;

CHsO ClC=C H2 Example 2 perature is kept below 42 C. by good cooling. After ture. The ortho-phosphoric acid triesters or thionophosr mixture in the conventional manner.

the reaction has ceased, the reactants are further stirred for 3 hours -at '45 C. The reaction mixture is cooled to room; temperature, 50 parts of water and parts of benzene are added thereto, stirred well and the-.layers separated. The aqueous layer is again extracted with 60 parts of benzene and the extracts combined with the non-aqueous layer. Thebenzene solution obtained is washed with 50 parts of water, dried over sodium sulfate and the solvent distilled off in vacuo. There remain as a residue 241 parts of a reddish, non-distillable oil of the following formula:

Example 3 56.4 parts of diethoxy-thionoph'osphoric acid chloride are allowed to. flow slowly into a mixture of 49;8 parts of 1-ethylmercapto-3-chlor-butene-(3)-o1-(2) and 23.7 parts of anhydrous pyridine with good stirring. The temperature is prevented from rising above about 40 C. by cooling. The reactants are stirred for an additional 4hours at 40 to 50 C. and worked up as specified in Example l After distilling off the solvent, there are ob tained 91 parts ofthe new thionophosphoric acid ester as a pale yellowish oil of the formula:

CaHaO S i 7 canto O CH+0Hz-SC,Ht v C1-C=CH2 Example 4 32.1}1 parts-of"dimethoxythionophosphoric acid monochlorid'e are allowed to flow at-30 'to 40 C. while stirring into a mixture of 33.3 parts of l-ethylmercapto- 3-chlor-butene-(3)-o1-(2) and 158 parts of pyridine. The whole is further stirred for 4 hours at 40 to 50 C. The reaction mixture is cooled and 80 parts of methylene chloride added. The solution obtained is extracted twice, each time with parts of water, and the organic layer is separated from the water and dried with sodium sulfate. The solvent is distilled oif in vacuo and 40 parts of the compound of the formula:

are obtained as a pale brown oil which can be distilled only with partial decomposition at the boiling point 95 to 100 C. at 0.5 mm. Hg pressure.

'By working as above but using 41 parts of dimethoxythionophosphoric acid monobromide instead of 32.1 parts of dimethoxythionophosphoric acid monochloride, 43 parts of the compound obtainable according to paragraph 1 of this example are obtained.

Example 5 are obtained as a yellowish oil which can be distilled only with marked decomposition.

Example 6 216 parts of dipropoxythionophosphoric acid chloride areslowly introduced at 40 to 45 C. with powerful stirring into a mixture of 166 parts of l-ethylmercapto- 3-chlor-butene-(3 )-ol-(2) and 79 parts of pyridine. After the introduction, thewhole is further stirred for 5 hours at 45 C. and the reaction mixture worked up as specified in Example 4. 295 parts of the compound of the formula:

CIC=CH2 are obtained as a yellowish oil.

Example 7- 163 parts of 1-normal-propylamino-3-ehlor-butene (3)-ol-(2) and 79 parts of pyridine are mixed and then at 30 to 40 C. while stirring 172 parts of diethoxyphosphoric acid chloride are allowed to flow in. The whole.

is further stirred for 4 hours at 50 C; and worked up as described in Example 2. 275 parts of the compound of the following formula are obtained as a pale oil:

36.3 parts of 1-amino-3-chlor-butene-(3)-ol-(2) and 23.7 parts of pyridine are well mixed and into the mixture 56.4 parts of diethoxythionophosphoric acid chloride are introduced at 45 to 50 C. while stirring powerfully. The stirring is continued for another 6 hours at 50 C., after which the reaction mixture is cooled and worked up as described in Example 2. 86 parts of a compound of the formula:

C5H50/ o' 'CH-"CHTNH2 V C1C=CHi are obtained.

Example 9 i 56.4 parts of diethoxythionophosphoric acid chlorid are allowed to flow at to C. while stirring well into a mixture of 48.3 parts of 1-ally1amino-3-chlorbutene-(3)-ol-(2) and 23.7 parts of pyridine. The reaction isstirred for another 5 hours at 50 C., cooled to room temperature and worked up as described in Example 2. 67 parts of a yellowish oil are obtained to which the following formula applies: 2

021150 O-GHGHg-NHCH CH=CH,

We claim: 1. The compound of the formula CzH5-O S oim-o OCHCHzS C2Hr 7. C1- =CH2 2. The compound of the formula 011 -0 s a r CHg-O OCHCH2S-C2H5 Cl- =CH:

3. The compound of the formula C2H5-O S can-o C zHr- O 6. A process for the production of 0.0.-dialkylphosphoric and 0.0-dialkylthionophosphoric acid esters of the general formula in which R and R' are alkyl groups with one to four C-atoms, X is an element of the group consisting of oxygen and sulfur, Z is a member of the class consisting of hydrogen and alkyl and alkenyl radicals with from one to four C-atoms, and Y is a member selected from '7 the group consisting of oxygen, sulfur, and the -'-NH-'-- group, which comprises reacting an 0.0.-dialkylphosphoric acid monohalide of the formula I RO/ Hal in which R and R are alkyl groups with one to four C-atoms, X is an element of the group consisting of oxygen and sulfur, and Hal is a halogen atom selected from the group consisting of chlorine and bromine with an equivalent amount of a l-substituted-3-chlorobutene- (3)-ol-(2) of the formula CHE-YZ in which Y and Z have the aforesaid significance, in the presence of an agent capable of binding hydrogen halide at a temperature of from to 120 C.

7. A process as claimed in claim 6 wherein the reaction is carried out in the presence of an inert organic medium.

8. A process for the production of O.O.-dialkylphosphoric and 0.0-dialkylthionophosphoric acid esters of the general formula.

in which R and R are alkyl groups with one to four butene-(3)-ol-'(2) of the formula (31 HOCHC=CH HPYZ in which Y and Z have the aforesaid significance, in the presence of an agent capable of binding hydrogen chloride at a temperature of from 15 to C.

9. The process as claimed in claim 6, wherein the reaction is carried out in the presence of an inert organic diluent.

10. A compound of the general formula in' which R and R are alkyl groups with one to four C-atoms, X is an element of the group consisting of oxygen and sulfur, Z is a member of the class consisting of hydrogen and alkyl and alkenyl radicals with from one to four C-atoms, and Y is a member selected from the group consisting of oxygen, sulfur, and the -NH- p- 7 11. A compound of the general formula o-cn-o=om in which R and R are alkyl groups with one to four C-atoms and Z is a member of the class consisting of hydrogen and alkyl and alkenyl radicals With from one to four C-atoms.

12. A compound of the general formula No references cited. 

6. A PROCESS FOR THE PRODUCTION OF A.O.-DIALKYLPHOSPHORIC AND O.O-DIALKYTHIONOPHOSPHORIC ACID ESTERS OF THE GENERAL FORMULA
 10. A COMPOUND OF THE GENERAL FORMULA 